Munroe's technique is a type of minimalism.
By drawing mostly in stick figures and simple forms, Munroe is giving you only what is needed to set the scene, similar to a theatrical production with minimal props, costumes, and sets. You get to use your imagination to fill in all the rest.
In the xkcd world, it doesn't particularly matter that Cueball has a simple circle for a head, with no facial features present, because Munroe's comedy is not primarily a visual type of comedy. The humor is found in the text, and in the situations he sets up, not in the facial expressions of the characters or in elaborately drawn backgrounds.
Which is not to say that the visuals don't matter. They certainly do. Looking at an xkcd strip is a lot different than reading the transcript on http://www.explainxkcd.com. But the way that they matter does not depend on them being drawn in a more elaborate style.